Dyestuffs of the naphthophenosafranine series



Patented Nov. 7, 1939 PATENT OFFICE DYESTUFFS OF THE NAPHTHOPHENO- SAFRANINE SERIES Eugen Huber, Leverkusen-I. G. Work, Germany, assignor to General Aniline Works, Inc, New- York, N. Y., a corporation of Delaware No Drawing. Application March 27, 1936, Serial No. 71,311 In Germany March 29, 1935 '7 Claims.

The present invention relates to new acid dyestufis of the naphthophenosafranin-e series and to a process for the manufacture of the said dyestuffs, more particularly it relates to dyestufis which may be represented by the probable general formula:

N N 20 16 g} -s 0311 R4 I alkyl 19 17 In the said formula R1 means alkyl or hydroaryl, R2 and R3 mean the same or different members selected-from the group consisting of hydrogen, alkyl, aralkyl and hydroaryl, and R4, R5 and Rs mean the same or different members selected from the group consisting of hydrogen, alkyl, alkoxy and halogen.

It is known from experience that it is only very difficultly possible to obtain, by sulfonating in the usual manner, sufiiciently soluble dyestufis from naphthophenosafranines which do not contain as substituents groups capable of being sul fonated, such as phenyl or benzyl radicals. In

order to obtain a sufficient solubility, it is ,necessary to apply very energetic sulfonating conditions, and in such cases very dull products are obtained, which are useless for technical purposes.

In accordance, with the present invention na phthophenosafranines which do not contain as substituents groups capable of being sulfonated, such as benzyl or phenyl radicals, can be easily sulfonated to useful and readily soluble azine dyestufis of good clearness, when the nucleus I of the first formula below is substituted, in suitable manner, by groups which are themselves not capable of being sulfonated.

The process of manufacture according to the present invention is by sulfonating dyestuffs of the following general formula:

r1 Rz Rs in which R1 means alkyl or hydroaryl, R2 and/or R3 mean hydrogen, alkyl or hydroaryl, R4, R5 and R6 mean hydrogen, alkyl, alkoxy or halogen, and the nucleus I contains at least one alkyl group. Particularly good results are obtained, when both the o-positions to the azine nitrogen are substituted by alkyl radicals. In cases where a free amino group is present in l8-position, it is advantageous that at least one of the two 0- positions to this amino group be substituted by an alkyl radical.

The sulfonation of the starting basic dyestuffs is performed in the usual manner, f. i. by introducing the basic dyestufi into oleum, for example an oleum containing 30-40% of S03, and sul-- ionating at temperatures, say between about 50 and about 100 C., until a test portion is clearly soluble in aqueous sodium acetate solution. Depending upon the different starting dyestuifs the process is complete between about 2 and about 6 hours. I

The basic naphthophenosafranines specified as starting materials can be obtained from isorosindulines or isorosinduline-6-su1fonic acid and p-phenylenediamines (for instance, according to British Patent No. 24,410/1897 and U. S. Patent No. 617,703).

The dyestuffs obtained according to this process are distinguished by remarkable clear blue shades. They are readily soluble and in general have a good equalizing capacity.

In cases where the amino group in l8-position,

is either unsubstituted or only mono-substituted,

the dyestuffs can be aftertreated with an alkylating, aralkylating, or acylating agent. Thus, for instance, by after-treatment of the sulfonated dyestuffs with benzyl chloride, dyestuffs of a remarkable fastness to washing, fulling and sea water are obtained.

The invention is illustrated by the following examples, but is not restricted thereto:

Example 1.The phenonaphthosafranine of 1 the formula:

HINQN N .N{C2 s) Ha H 0 CH is introduced, for sulfonation, into five times the quantity of fuming sulfuric acid of 30% strength, and heated at 80 C., during several hours, until a test portion is soluble to a clear solution in an aqueous solution of sodium acetate. The sulfom'c groups probably enter the 12- and lfi-positions. The working up is effected by pouring on ice, filtration, and converting into the sodium salt. The dyestuffs obtained dyes wool very clear greenish blue shades of good fastness to light and alkalies. By heating with benzyl chloride, in an aqueous or dilute alcoholic solution, in the presence of sodium acetate, the amino group in the l8-position is benzylated, whereby an excellent fastness to sea water is obtained. The dyestuff probably corresponds to the following formula:

HaCgCHmHNQN H3 S OaH HaC CH:

SOsH

Example 2.In an analogous manner to that described in Example 1 the dyestufi of the formula:

enter the 12- and 16-positions. The dyestuff dyes wool clear and somewhat more reddish shades than the dyestuff obtained according to the Example 1.

properties.

Ithas likewise good fastness In an analogous manner there has been prepared the dyestuff of the following constitution:

0H: I HINQN \N M02115),

Hi s 08H SOaH and the dyestufi of the following constitution:

(IJHa H3O S 0311 HaC CH3 S0311; 3. which dye wool greenish blue shades. The positions of the ethyl or isopropyl group, respectively,

N CH:

| H NQN= F N-(CgHs);

is sulfonated. Probably the sulfonic acid groups enter the 12- and lfi-positions. The dyestuff obtained directly and also that obtained after benzylation have a great similarity to the products obtained according to the Example 1.

Example 4.-For sulfonation, the dyestuff of the formula:

is heated at 0., during several hours, with five times the quantity of fuming sulfuric acid, until a test portion dissolves in a dilute sodium acetate solution without a residue. The Working-up and conversion into the sodium salt are efiected in the usual manner. The dyestuif dissolves with a green coloration in concentrated sulfuric acid, with a blue coloration in water, and dyes wool clear and greenish blue shades of good fastness to light and alkalies. It has a good equalizing capacity. The dyestufi has probably the following formula:

Example 5.The dyestuff obtained in an analogous manner to that described in Example 4, which has probably the formula:

dyes wool somewhat more reddish shades of equal fastness properties.

Example 6.In an analogous manner to that indicated in Example 4, a dyestufi which probably has the constitution:

I 1 e a HaC- 3 SOaH is obtained. It dyes wool blue shades which are not quite so clear as those of the dyestufis of the preceding examples, but have good fastness to light and alkalies.

Example 7.In an analogous manner to that described in Example 4, the dyestuif probably of the formula:

l S 03H HaC- -SO3H is obtained. It dyes wool clear greenish blue shades of good fastness to light and alkalies and has a goodequalizing capacity.

Example 8.The dyestuff probably of the formula:

manufactured in an analogous manner to that described in Example 1, by sulfonating and benzylating, dissolves with a green coloration in concentrated sulfuric acid, in water with a clear greenish blue coloration, and dyes wool clear and greenish blue shades of good fastness to light,

alkalies, washing, and sea water.

Instead of the benzyl radical, with the same success, the 2-ch10r0- or 2.4-dichloro-benzyl radical may be introduced.

Example 9.--The dyestuif probably of the formula:

manufactured in an analogous manner to that described in Example 4, dissolves With'a green coloration in concentrated sulfuric acid, with a blue coloration in water, and dyes wool clear and greenish blue shades of good fastness to light and alkalies and of a good equalizing capacity.

Emample 10.-'I-he dyestuff probably of the manufactured in a similar manner to that described in Example 9, has similar properties to the dyestuff of Example 9.

Example 11.The dyestufi probably of the formula:

- the formula:

Nom),

SOaH

Example 13.The dyestuff probably of the formula:

C 4H9 CsH5.CHz.HN I N- is manufactured in a similar manner to the dyestuff described in Example 1. It is equal to the dyestuff of Example 1 in shade and properties.

Example 14.-In an analogous manner to that described in Example 1, the dyestufi probably of C 0115. C HLHN is obtained. It has similar properties to the dyestuff described in Example 13.

Example 15.The isorosinduline obtained, in an analogous manner to that described in Example 4, from o-tolyl-fi-naphthylamine and nitrosodibutylaniline is oxidized together with xylylene-diamine, and the safranine obtained is sulfonated in the known manner. The dyestuff obtained dyes wool clear and blue shades of good fastness to alkalies, light and washing It has probably the formula:

'N/ I I H3O S 03H SOaH Example 16.The isorosinduline obtained from Vic. m-xylyl-B-naphthylamine and nitroso-cyclohexyl-ethylaniline is oxidized together with xylylene diamine, and the safranine obtained is sulfonated in the known manner.

The dyestufi obtained, probably of the for-,-

m ,o I) Q can Ha 03H dyes wool reddish blue shades of good fastness to alkalies and light. I r Y Example 17.Theisorosindu1ine obtained in an analogous manner to that described in Example 4, from p-xylyl-c-naphthylamine and nitrosodiethylaniline is oxidized with 5-aminocyclohexyl- 2-toluidine, and the dyestuff obtained is sulfonated. It dissolves with a green coloration in concentrated sulfuric acid, with a clear greenish blue coloration in water, and dyes wool clear and blue shades of good fastness to light, alkalies and Washing.

The dyestuif probably has the formula:

Example 18.The isorosinduline obtained from m-tolyl-B-naphthylamine and nitroso-diethylaniline is converted with bisulfite into the 6-monosulfonic acid, and the latter is treated in a diluted alcoholic solution with xylylenediamine. The basic safranine thus obtained is sulfonated by heating during several hours with five parts of fuming sulfuric acid of 32% strength.

The dyestuff probably has the formula:

HOaS- It dissolves with a green coloration in concentrated sulfuric acid, with a blue coloration in water, and dyes Wool blue shades of good fastness properties.

Example 19.The dyestuff of the formula:

N CH3 H2N-N= I M ms):

('11 SOKH has similar properties to the dyestufi obtained according to Example 18.

Example 20.The isorosinduline obtained from 6 methoxy -3- methylphenyl 6 naphthylamine gives by oxidizing together with xylylenediamine and subsequent sulfonation, in an analogous manner to that described in Example 1, a dyestufl probably of the constitution:

HzN-QN: N/ N(C2H5)2 I H30 03H OCH 3 SO3H It dissolves with a greenish coloration in concentrated sulfuric acid, with a blue coloration in water, and dyes wool reddish blue shades of good fastness properties.

I claim:

1. The process which comprises sulfonating a dyestuff of the following general formula:

75 wherein R1 means a member of the group consisting of alkyl and cyclohexyl, R2 and R3 mean the same or different members selected'from the group consisting of hydrogen, alkyl and cyclohexyl, and R4, R5 and Rs mean the same or different members selected from the group consisting of hydrogen, alkyl, alkoXy and halogen, until a test portion is soluble in aqueous sodium acetate solution. a n

2. The process which comprises sulfonating a dyestuif of the following general formula:

moumQ-ru N40230:

H30- CH until a test portion is soluble in aqueous sodium acetate solution.

4. The process which comprises sulfonating the dyestufi of the following formula:

N CH3 l HaCLHN-O-N N{CH:):

until a test portion is soluble in aqueous sodium acetate solution.

v 25 CHa-HNQN 5. The dyestuff having in its free state the following formula:

15 dyeing W001 clear greenish blue shades of good fastness to light and alkalies.

6. The dyestufi having in its free state the following formula:

1O CH3 SOaH dyeing wool clear blue shades of good fastness to light and alkalies.

7. Dyestuffs having in the free state the general formula wherein Rr'stands for a member of the group consisting of hydrogen, alkyl and aralkyl, and R2 and Rs mean the same or different members selected from the group consisting of hydrogen,

and methyl, yielding on animal fibers in general clear blue shades.

EUGEN HUBER. 

